Azeotrope-like compositions of cis-1,1,1,4,4,4-hexafluoro-2-butene

ABSTRACT

This invention relates to azeotrope-like compositions, methods and systems having utility in numerous applications, and in particular, uses for azeotrope-like compositions comprising effective amounts of the compound cis-1,1,1,4,4,4-hexafluoro-2-butene (Z-HF0-1336mzzm), which has the following structure: 
     
       
         
         
             
             
         
       
     
     and another material selected from the group consisting of water, fluoroketones, alcohols, hydrochlorofluoroolefins, and combinations of two or more thereof. These compositions may be used in a wide variety of applications such as, blowing agents, refrigerants, heating agents, power cycle agents, cleaning agents, aerosol propellants, sterilization agents, lubricants, flavor and fragrance extractants, flammability reducing agents, and flame suppression agents.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a division of U.S. application Ser. No. 14/502,324,filed Sep. 30, 2014, which application is a division of U.S. applicationSer. No. 12/967,522, filed Dec. 14, 2010, now U.S. Pat. No. 8,846,754,issued on Sep. 30, 2014, which application claims benefit of U.S.Provisional Patent Application No. 61/287,041 filed Dec. 16, 2009, thedisclosure of which is hereby incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to azeotrope-like compositions, methods andsystems having utility in numerous applications, and in particular, usesfor azeotrope-like compositions comprising, or consisting essentiallyof, effective amounts of the compoundcis-1,1,1,4,4,4-hexafluoro-2-butene (Z-HF0-1336mzzm), which has thefollowing structure:

and another material selected from the group consisting of water,fluoroketones, alcohols, hydrochlorofluoroolefins, and combinations oftwo or more thereof.

BACKGROUND OF THE INVENTION

The azeotrope-like compositions of the present invention are part of acontinued search for the next generation of low global warming potentialmaterials. Such materials must have low environmental impact, asmeasured by ultra-low global warming potential and near zero ozonedepletion potential.

The azeotrope-like compositions of the present invention may be used ina wide variety of applications such as blowing agents, refrigerants,heating agents, power cycle agents, cleaning agents, aerosolpropellants, sterilization agents, lubricants, flavor and fragranceextractants, flammability reducing agents, and flame suppression agents,to name a few preferred uses.

SUMMARY OF THE INVENTION

Applicants have developed several azeotrope-like compositions whichinclude as an essential component Z-HFO-1336mzzm. In certainembodiments, the other part of the azeotrope-like composition is atleast one C1 to C12 alcohol compound. In other embodiments, the otherpart of the azeotrope-like composition is water. In other embodiments,the other part of the azeotrope-like composition is a fluoroketonecompound. In other embodiments, the other part of the azeotrope-likecomposition is a hydrochlorofluoroolefin compound.

According to certain embodiments, the present invention providesazeotrope-like compositions comprising, or preferably consistingessentially of, from greater than zero to about 99 wt % of the compoundZ-HFO-1336mzzm and from about 1 wt % to less than 100 wt % of analcohol, and combinations of two or more thereof. Preferred alcohols arethe C1 to C12 alcohols. Especially preferred are methanol and ethanol.

It should be noted that it would be common and expected for a productdesignated as Z-HFO-1336mzzm to include a minor percentage, for exampleabout 0.5 wt % up to about 5 wt % of other components, includingparticularly E-HF0-1336mzzm. When used herein, the term “consistingessentially of Z-HFO-1336mzzm” is intended to generally include suchcompositions. The terms “consist of” and “consisting” of as used herein,do not include such other components. All of the embodiments of theinvention described herein may, if desired, be obtained in asubstantially purified form, such that these embodiments preferablyconsist of only the actual components designated, other than minor(e.g., ppm) impurities.

The present invention preferably provides azeotrope and azeotrope-likecompositions comprising, or preferably consisting essentially of,Z-HFO-1336mzzm/ethanol or Z-HF0-1336mzzm/methanol. Preferably, theazeotrope-like compositions of the present invention comprise, or morepreferably consist essentially of, effective amounts of Z-HFO-1336mzzmand ethanol or Z-HFO-1336mzzm and methanol. The term effective amount,as used herein, refers to the amount of each component which uponcombination with the other component or components, results in theformation of the present azeotrope-like compositions.

In certain embodiments the azeotrope-like composition comprises, orpreferably consists essentially of, from about 75 wt % to less than 100wt % of Z-HFO-1336mzzm and from greater than zero to about 25 wt % of analcohol, and combinations of two or more thereof.

In other embodiments, the azeotrope-like composition comprises, orpreferably consists essentially of, from about 85 wt % to less than 100wt % of Z-HFO-1336mzzm and from greater than zero to about 15 wt % of analcohol, and combinations of two or more thereof.

Another embodiment of the present invention is directed toazeotrope-like compositions comprising from greater than zero to about99 wt % of the compound water and from about 1 wt % to less than 100 wt% of Z-HFO-1336mzzm.

In certain embodiments the azeotrope-like composition comprises, orpreferably consists essentially of, from greater than zero to about 50wt % of water and from about 50 wt % to less than 100 wt % ofZ-HFO-1336mzzm.

In other embodiments, the azeotrope-like composition comprises, orpreferably consists essentially of, from greater than zero to about 10wt % of water and from about 90 wt % to less than 100 wt % ofZ-HFO-1336mzzm.

One embodiment of the invention is a blowing agent comprising, orconsisting essentially of, one or more of the azeotrope-like compositionof the present invention.

Another embodiment of the invention is a method of forming a foamcomprising adding to a foamable composition a blowing agent comprising,or consisting essentially of one or more of the azeotrope-likecompositions of the present invention. The blowing agent may furthercomprise a premix of a polyol and the blowing agent, wherein the blowingagent comprises an azeotrope-like composition of the present invention.

Yet another embodiment of the invention is a closed cell foam preparedby foaming a foamable composition in the presence of a blowing agentcomprising, or consisting essentially of, one or more of theazeotrope-like compositions of the present invention. Preferably, theclosed cell foam is formed from a foamable composition that furthercomprises polyurethane, polyisocyanurate, polystyrene, polyethylene, andmixtures thereof.

One embodiment of the invention is a refrigerant composition comprising,or consisting essentially of, one or more of the azeotrope-likecompositions of the present invention. Another embodiment of theinvention is a refrigeration system comprising a refrigerant compositionof the present invention. Yet another embodiment of the invention is amethod for cooling an article which comprises evaporating a refrigerantcomposition of the invention in the vicinity of the article to becooled.

Another embodiment of the invention is a method for heating an articlewhich comprises condensing a refrigerant composition comprising, orconsisting essentially of, one or more of the azeotrope-likecompositions of the present invention in the vicinity of the article tobe heated.

One embodiment of the invention is a sprayable composition comprising amaterial to be sprayed and a propellant comprising, or consistingessentially of, one or more of the azeotrope-like compositions of thepresent invention.

Yet another embodiment of the invention is a method of reducing theflammability of a fluid comprising adding one or more of theazeotrope-like compositions of the present invention to said fluid.

Another embodiment of the invention is a method of suppressing a flamecomprising contacting said flame with a fluid comprising one or more ofthe azeotrope-like compositions of the present invention. Optionally,this fluid may further include one or more fluoroketone compounds. Onepreferred fluoroketone compound is dodecafluoro-2-methylpentan-3-one.One source for this compound is the 3M Company under the brand nameNovec 1230.

Yet another embodiment of the invention is a method of cleaning and/orsterilizing an article, said method comprising contacting said articleto be cleaned or sterilized with a composition comprising, or consistingessentially of, one or more of the azeotrope-like compositions of thepresent invention. Optionally, the composition may further includeethylene oxide.

Azeotrope-Like

The term azeotrope-like refers to compositions that behave likeazeotropic mixtures, that is, the composition of the vapor formed duringboiling or evaporation is identical, or substantially identical, to theoriginal liquid composition. Thus, with boiling or evaporation, theliquid composition changes, if at all, only to a minimal or negligibleextent. This is to be contrasted with non-azeotrope-like compositions inwhich, during boiling or evaporation, the liquid composition changes toa substantial degree.

The term azeotrope-like is thus intended in its broad sense to includeboth compositions that are strictly azeotropic and compositions thatbehave like azeotropic mixtures. From fundamental principles, thethermodynamic state of a fluid is defined by pressure, temperature,liquid composition, and vapor composition. An azeotropic mixture is asystem of two or more components in which the liquid composition andvapor composition are equal at the state pressure and temperature. Inpractice, this means that the components of an azeotropic mixture areconstant boiling and cannot be separated during a phase change.

The term “azeotrope-like” especially refers to a combination of thecompound Z-HF0-1336mzzm with one or more compounds that behavesubstantially like a single compound in so far as the vapor insubstantial equilibrium with the liquid has substantially the sameconcentration of components present in the liquid.

Azeotropes-like compositions according to the present invention includeabsolute azeotropes (compositions in which azeotropic conditions aresatisfied, at a particular pressure, over all values of temperature (upto the critical stage)) or limited azeotropes (compositions in whichazeotropic conditions are satisfied only in a certain temperature rangeat a particular pressure). Azeotropes-like compositions according to thepresent invention also include homo-azeotropes, wherein, at a givenpressure, the composition exists in a single liquid phase, orhetero-azeotropes, wherein, at a given pressure, the composition existsas two or more liquid phases. Moreover, azeotrope-like compositionsaccording to the present invention can be binary, ternary, quaternary,or quinary azeotropes depending on whether the composition is composedof 2, 3, 4, or 5 compounds, respectively (or more).

As described above, the azeotrope-like compositions of the invention areconstant

The azeotrope-like compositions of the invention may include additionalcomponents that do not form new azeotrope-like systems, or additionalcomponents that are not in the first distillation cut. The firstdistillation cut is the first cut taken after the distillation columndisplays steady state operation under total reflux conditions. One wayto determine whether the addition of a component forms a newazeotrope-like system so as to be outside of this invention is todistill a sample of the composition with the component under conditionsthat would be expected to separate a non-azeotropic mixture into itsseparate components. If the mixture containing the additional componentis non-azeotrope-like, the additional component will fractionate fromthe azeotrope-like components. If the mixture is azeotrope-like, somefinite amount of a first distillation cut will be obtained that containsall of the mixture components that is constant boiling or behaves as asingle substance.

It follows from this that another characteristic of azeotrope-likecompositions is that there is a range of compositions containing thesame components in varying proportions that are azeotrope-like orconstant boiling. As used herein, “constant boiling” means that theboiling point of the composition does not vary by no more than about ±2°C., preferably by no more than about ±1° C., more preferably by no morethan about ±0.5° C., and most preferably by no more than about ±0.2° C.over a change of the azeotrope-like composition. All such compositionsare intended to be covered by the terms “azeotrope-like” and “constantboiling.” As an example, it is well known that at differing pressures,the composition of a given azeotrope will vary at least slightly, asdoes the boiling point of the composition.

As described above, the azeotrope-like compositions of the invention areconstant boiling or essentially constant boiling. In other words, forthese azeotrope-like compositions, the composition of the vapor formedduring boiling or evaporation is identical, or substantially identical,to the original liquid composition. Thus, with boiling or evaporation,the liquid composition changes, if at all, only to a minimal ornegligible extent. This is to be contrasted with non-azeotrope-likecompositions in which, during boiling or evaporation, the liquidcomposition changes to a substantial degree.

Thus, an azeotrope-like composition of component A and component Brepresents a unique type of relationship, but with a variablecomposition depending on temperature and/or pressure. It follows that,for azeotrope-like compositions, there is a range of compositionscontaining the same components in varying proportions that areazeotrope-like. All such compositions are intended to be covered by theterm azeotrope-like as used herein.

The preferred azeotrope-like compositions of the present invention areenvironmentally acceptable and do not to contribute to the depletion ofthe earth's stratospheric ozone layer. The compounds and compositions ofthe present invention have no substantial ozone depletion potential(ODP), preferably an ODP of not greater than about 0.5 and even morepreferably an ODP of not greater than about 0.25, most preferably an ODPof not greater than about 0.1; and/or a global warming potential (GWP)of not greater than about 150, and even more preferably, a GWP of notgreater than about 50. Preferably, both criteria are met by thecompositions.

As used herein, ODP is defined in the “Scientific Assessment of OzoneDepletion, 2002,” a report of the World Meteorological association,incorporated here by reference.

As used herein, GWP is defined relative to that of carbon dioxide andover a 100 year time horizon, and defined in the same reference as forthe ODP mentioned above.

In one preferred embodiment, the present invention providesazeotrope-like compositions comprising, or preferably consistingessentially of, Z-HF0-1336mzzm and ethanol. Another preferred embodimentof the present invention provides the azeotrope-like compositionscomprising, or preferably consisting essentially of, Z-HF0-1336mzzm andmethanol. Other alcohols can likewise be employed, such as propanol,butanol, pentanol, hexanol, octanol, nonanal, decanol, and the like.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 illustrates k factors of polyurethane foams.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In the azeotrope-like compositions of the present invention, the amountof the Z-HF0-1336mzzm may vary widely, including in all casesconstituting the balance of the composition after all other componentsin composition are accounted for.

As described above, methanol and ethanol are preferred alcohols employedin preferred azeotrope-like compositions of the present invention. Theseembodiments preferably provide azeotrope-like compositions comprising,and preferably consisting essentially of, from greater than zero toabout 50 parts by weight ethanol, and from about 50 to less than 100parts by weight of Z-HFO-1336mzzm, more preferably from greater thanzero to about 20 parts by weight ethanol, and from about 80 to less than100 parts by weight of Z-HFO-1336mzzm, and even more preferably fromgreater than zero to about 10

These embodiments preferably provide azeotrope-like compositionscomprising, and preferably consisting essentially of, from about 1 toabout 50 parts by weight methanol, and from about 50 to about 99 partsby weight of Z-HFO-1336mzzm, more preferably from about 1 to about 70parts by weight methanol, and from about 30 to about 99 parts by weightof Z-HFO-1336mzzm, and even more preferably from about 1 to about 85parts by weight methanol, and from about 15 to about 99 parts by weightof Z-HF0-1336mzzm. Preferred compositions of the present invention arecharacterized by a boiling point of about 29.7° C., preferably ±2° C.,more preferably ±1° C. at 14.3 psia.

Additional components may be added to tailor the properties of theazeotrope-like compositions of the invention as needed. By way ofexample, oil solubility aids may be added in the case in which theazeotrope-like compositions of the invention are used as refrigerants.Stabilizers and other materials may also be added to enhance theproperties of the azeotrope-like compositions of the invention.

The ethanol or methanol can be removed from the azeotrope using anextractant such as water. Due to each alcohol's high solubility in waterthe alcohol will be removed to the aqueous phase and the Z-HFO-1336mzzmwill phase separate from the aqueous phase leaving behind a purifiedZ-HFO-1336mzzm. The alcohol can then be extracted from the water usingcommon drying techniques such as a molecular sieve.

Other embodiments preferably provide azeotrope-like compositionscomprising, and preferably consisting essentially of, from about 1 toabout 50 parts by weight water, and from about 50 to about 99 parts byweight of Z-HFO-1336mzzm, more preferably from about 10 to about 40parts by weight water, and from about 60 to about 90 parts by weight ofZ-HFO-1336mzzm, and even more preferably from about 15 to about 35 partsby weight water, and from about 65 to about 85 parts by weight ofZ-HFO-1336mzzm. Preferred compositions of the present invention arecharacterized by a boiling point of about 31.4° C., preferably ±2° C.,more preferably ±1° C. at 14.5 psia.

Other embodiments preferably provide azeotrope-like compositionscomprising, and preferably consisting essentially of, from about 1 toabout 50 parts by weight of the fluoroketonedodecafluoro-2-methylpentan-3-one, and from about 50 to about 99 partsby weight of Z-HFO-1336mzzm, more preferably from about 5 to about 45parts by weight Novec 1230, and from about 55 to about 95 parts byweight of Z-HFO-1336mzzm, and even more preferably from about 10 toabout 30 parts by weight of the fluoroketone, and from about 70 to about90 parts by weight of Z-HFO-1336mzzm. Preferred compositions of thepresent invention are characterized by a boiling point of about 32.0°C., preferably ±2° C., more preferably ±1° C. at 14.5 psia.

Compositions according to the present invention, including the preferredazeotrope-like compositions, may include one or more components, such asadditives, which may not form new azeotrope-like compositions. Knownadditives may be used in the present compositions in order to tailor thecomposition for a particular use Inhibitors may also be added to thepresent compositions to inhibit decomposition, react with undesirabledecomposition products, and/or prevent the corrosion of metal surfaces.Typically, up to about 2 percent of an inhibitor based on the totalweight of the azeotrope-like composition may be used.

Azeotrope Additives

The azeotrope-like compositions of the present invention may furtherinclude any of a variety of optional additives including stabilizers,metal passivators, corrosion inhibitors, and the like.

According to certain embodiments, the azeotrope-like compositions of thepresent invention further comprise a stabilizer. Any of a variety ofcompounds suitable for stabilizing an azeotrope-like composition of thepresent invention may be used. Examples of certain preferred stabilizersinclude stabilizer compositions comprising at least one phenolcomposition and at least one epoxide selected from the group consistingof aromatic epoxides, alkyl epoxides, alkenyl epoxides, and combinationsof two or more thereof. The stabilizer mixture may further be comprisedof nitromethane, 1,2-butylene oxide and 1,3-dioxolane or 1,4-dioxane. Ithas also been found that various terpene hydrocarbons and terpenealcohols as well as mineral spirits, glycol ethers, alcohols, andketones can be used in conjunction with the above identified stabilizermixture.

Any of a variety of phenol compounds is suitable for use in the presentcompositions. While applicants do not wish to be bound by or to anytheory of operation, it is believed that the phenols act as radicalscavengers in the azeotrope-like compositions and thereby tend toincrease the stability of such compositions. As used herein the termphenol compound refers generally to any substituted or unsubstitutedphenol. Examples of suitable phenol compounds include phenols comprisingone or more substituted or unsubstituted cyclic, straight-chain, orbranched aliphatic substituent group, such as, alkylated monophenolsincluding: 2,6-di-tert-butyl-4-methylphenol;2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol;tocopherol; and the like, hydroquinone and alkylated hydroquinonesincluding: t-butyl hydroquinone; other derivatives of hydroquinone; andthe like, hydroxylated thiodiphenyl ethers including:4,4′-thiobis(2-methyl-6-tert-butylphenol);4,4′-thiobis(3-methyl-6-tert-butylphenol);2,2′-thiobis(4-methyl-6-tert-butylphenol); and the like,alkylidene-bisphenols including:4,4′-methylenebis(2,6-di-tert-butylphenol);4,4′-bis(2,6-di-tert-butylphenol; derivatives of 2,2- or4,4-biphenyldiols; 2,2′-methylenebis(4-ethyl-6-tertbutylphenol);2,2′-methylenebis(4-methyl-6-tert-butylphenol);4,4,-butylidenebis(3-methyl-6-tert-butylphenol);4,4,-isopropylidenebis(2,6-di-tert-butylphenol);2,2′-methylenebis(4-methyl-6-nonylphenol);2,2′-isobutylidenebis(4,6-dimethylphenol);2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2- or4,4-biphenyldiols including2,2′-methylenebis(4-ethyl-6-tertbutylphenol), butylated hydroxy toluene(BHT), bisphenols comprising heteroatoms including:2,6-di-tert-.alpha.-dimethylamino-p-cresol;4,4-thiobis(6-tert-butyl-m-cresol); and the like; acylaminophenols;2,6-di-tert-butyl-4(N,N′-dimethylaminomethylphenol); sulfides including:bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide;bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; and the like; as well as,phenolic UV absorb and light stabilizers.

Certain preferred phenols include alkylated monophenols such astocopherol, BHT, hydroquinones, and the like. Certain particularlypreferred phenols include tocopherol, and the like. Most phenols arecommercially available. A single phenol compound and/or mixtures of twoor more phenols may be used in the present compositions. Any of avariety of epoxides will be suitable for use in the azeotrope-likecompositions of the present invention. While applicants do not wish tobe bound by or to any theory of operation, it is believed that theepoxides of the present invention act as acid scavengers in theazeotrope-like compositions and thereby tend to increase the stabilityof such compositions. A single aromatic epoxide and/or mixtures of twoor more aromatic epoxides may be used in the present compositions.

In certain other preferred embodiments, the alkyl epoxide for use as anacid scavenger in the present composition comprises polypropylene glycoldiglycidyl ether. Examples of polypropylene glycol diglycidyl ethersuitable for use in the present invention include the ether availablecommercially from SACHEM, Europe.

In addition, in certain embodiments, the epoxide for use in the presentinvention comprises combinations of two or more aromatic, alkyl, and/oralkenyl substituents. Such epoxides are referred to generally as“multisubstituted epoxides.” According to certain preferred embodiments,the stabilizer for use in the present invention comprises a combinationof at least one phenol compound and at least one aromatic, alkyl, oralkenyl epoxide. Examples of suitable combinations include stabilizerscomprising: tocopherol and allyl glycidyl ether, BHT and glycidyl butylether, and the like. Certain particularly preferred combinations includestabilizers comprising: tocopherol and allyl glycidyl ether, and thelike.

Any suitable relative amount of the at least one phenol compound and theat least one aromatic, alkyl, or alkenyl epoxide may be used in thepreferred stabilizers. For example, the weight ratio of phenolcompound(s) to aromatic or fluorinated alkyl epoxide(s) can be variedfrom about 1:99 to about 99:1. In certain preferred embodiments, theweight ratios of phenol compound(s) to aromatic, alkyl, alkenyl,multisubstituted, or fluorinated alkyl epoxide(s) is from about 30 toabout 1, more preferably from about 7 to about 1, more preferably fromabout 2 to about 1, and even more preferably about 1:1.

Azeotrope Examples Example 1

A sample of 69.4 wt % Z-HFO-1336mzzm, 3.1 wt % ethanol, 7.6 wt % lightsand remainder heavies was charged into a Monel distillation column. Thedistillation column is a spinning band column that operated atatmospheric pressure. The condenser was cooled using a thermostatedpropylene glycol water solution.

The distillation column was initially operated at full reflux andallowed to reach temperature and pressure equilibrium at each of thedesired conditions. Once the column had achieved equilibrium a vaporsample was taken from the overhead of the distillation column. Theoverhead of the column was periodically sampled as the distillate wascollected. After the lights had been removed from the distillationcolumn a sample was taken. The sample showed 2.0 wt % ethanol in theZ-HFO-1336mzzm. The ethanol persisted through the Z-HF0-1336mzzm cutindicating that an azeotrope had been formed.

Example 2

An ebulliometer was used to measure the azeotrope of Z-HFO-1336mzzm andethanol. The ebulliometer consist of a vacuum insulated glass vesselwhich is sealed at the bottom and open to the atmosphere at the top. Thetop or condenser portion of the ebulliometer is surrounded by dry ice toensure that all vapors are condensed and allowed to flow back into theebulliometer. Initially Z-HF0-1336mzzm was charged into the ebulliometerand ethanol was metered in.

Table 1 shows a minimum in temperature which indicates that an azeotropehas been formed. The bubble point temperature of the mixture remainsconstant indicating that this mixture is azeotrope-like over a largecomposition range.

TABLE 1 Ebulliometer measurements of Z-HFO-1336mzzm and Ethanol at 14.3psia Z-HFO- 1336mzzm, Ethanol, Temp, wt % wt % ° C. 100.00 0.00 31.699.59 0.41 31.3 97.97 2.03 31.2 95.65 4.35 31.1 93.43 6.57 31.1 89.9510.05 31.1 84.30 15.70 31.2 79.32 20.68 31.3 74.90 25.10 31.3 70.5329.47 31.3 66.64 33.36 31.4 63.15 36.85 31.4

Example 2

An ebulliometer as in Example 2 was used to measure the azeotrope ofZ-HFO-1336mzzm and methanol. Initially Z-HF0-1336mzzm was charged intothe ebulliometer and methanol was metered in.

Table 2 shows a minimum in temperature which indicates that an azeotropehas been formed. The bubble point temperature of the mixture remainsconstant indicating that this mixture is azeotrope-like over a largecomposition range.

TABLE 2 Ebulliometer measurements of Z-HF0-1336mzzm and Methanol at 14.3psia Z-HFO- 1336mzzm, Methanol, Temp, wt % wt % ° C. 100.00 0.00 32.0299.59 0.41 30.81 98.78 1.22 29.92 97.20 2.80 29.68 94.19 5.81 29.6691.35 8.65 29.66 86.17 13.83 29.78 81.55 18.45 29.80 77.39 22.61 29.9073.19 26.81 29.94 69.43 30.57 29.99 66.03 33.97 30.14 62.96 37.04 30.2460.15 39.85 30.44

Example 3

An ebulliometer as used in Example 2 was used to measure the azeotropeof Z-HF0-1336mzzm and dodecafluoro-2-methylpentan-3-one (Novec 1230).Initially Z-HF0-1336mzzm was charged into the ebulliometer and thefluoroketone Novec 1230 (3M Company) was metered in.

Table 3 shows a minimum in temperature which indicates that an azeotropehas been formed. The bubble point temperature of the mixture remainsconstant indicating that this mixture is azeotrope-like over a largecomposition range.

TABLE 3 Ebulliometer measurements of Z-HFO-1336mzzm and Novec 1230 at14.5 psia Z-HFO- 1336mzzm, wt % NOVEC 1230, wt % Temp, ° C. 100.00 0.0032.7 99.25 0.75 32.6 97.77 2.23 32.4 94.95 5.05 32.2 89.78 10.22 32.082.99 17.01 32.0 75.39 24.61 32.1 69.06 30.94 32.1 63.72 36.28 32.258.61 41.39 32.4 54.27 45.73 32.5 50.52 49.48 32.7 47.26 52.74 32.844.39 55.61 33.0

Example 4

The compound E-HCF0-1233zd (trans-1,1,1-trifluoro-3-chloropropene) hasalso been found to form an azeotrope-like composition withZ-HF0-1336mzzm. As shown below in Table 4, it has been found that theazeotrope-like properties of this composition continue up to about 10 wt% Z-HF0-1336mzzm. These compositions are especially useful for sprayfoam applications.

TABLE 4 Ebulliometer measurements of Z-HFO-1336mzzm and E-HCFO-1233zd at14.5 psia Ebulliometer study of 1233zd (E)/1336mzzm (Z) wt % wt % 1233zd(E) 1336mzzm (Z) Temp. (° C.) 100.00 0.00 17.70 99.60 0.40 17.70 98.821.18 17.73 97.28 2.72 17.75 95.79 4.21 17.81 92.95 7.05 17.89 87.7412.26 18.02 83.64 16.36 18.18 79.39 20.61 18.37 75.56 24.44 18.56 72.0827.92 18.76 68.91 31.09 18.98 65.66 34.34 19.18 62.70 37.30 19.36 59.9940.01 19.54 57.88 42.12 19.58 42.93 57.07 20.90 35.54 64.46 21.81 25.8074.20 23.22 15.66 84.34 25.13 4.67 95.33 30.44 0.18 99.82 32.79 0.00100.00 32.81

Example 5

An ebulliometer as in Example 2 was used to measure the azeotrope ofZ-HFO-1336mzzm and water. Initially Z-HF0-1336mzzm was charged into theebulliometer and water was metered in. Table 5 shows a minimum intemperature which indicates that an azeotrope has been formed. Thebubble point temperature of the mixture remains constant indicating thatthis mixture is azeotrope-like over a large composition range.

TABLE 5 Ebulliometer measurements of Z-HFO-1336mzzm and water at 14.5psia Z-HF0-1336mzzm, wt % Water, wt % Temp, ° C. 100.0 0.0 32.4 99.4 0.632.3 98.2 1.8 32.0 97.1 2.9 31.8 96.0 4.0 31.7 93.9 6.1 31.5 89.8 10.231.4 82.8 17.2 31.4 76.7 23.3 31.4 71.5 28.5 31.4 66.9 33.1 31.4 62.937.1 31.4 59.4 40.6 31.4

Uses of the Azeotrope-Like Compositions

As described above, any of the azeotrope-like compositions of theinvention may be used in a wide variety of applications as substitutesfor CFCs and for compositions containing less desirable HCFCs.

Specifically, the azeotrope-like compositions comprising, or consistingessentially of, effective amounts of Z-HFO-1336mzzm and another materialselected from the group consisting of water, fluoroketones, alcohols,hydrochlorofluoroolefins, and combinations of two or more thereof, areuseful as blowing agents, refrigerants, heating agents, power cycleagents, cleaning agents, aerosol propellants, sterilization agents,lubricants, flavor and fragrance extractants, flammability reducingagents, and flame suppression agents, to name a few preferred uses. Eachof these uses will be discussed in greater detail below.

Blowing Agents

One embodiment of the present invention relates to a blowing agentcomprising one or more of the azeotrope-like compositions of theinvention. In other embodiments, the invention provides foamablecompositions, and preferably polyurethane and polyisocyanurate foamcompositions, and methods of preparing foams. In such foam embodiments,one or more of the azeotrope-like compositions, are included as ablowing agent in a foamable composition, which composition preferablyincludes one or more additional components capable of reacting andfoaming under the proper conditions to form a foam or cellularstructure, as is well known in the art.

The present methods preferably comprise providing such a foamablecomposition and reacting it under conditions effective to obtain a foam,and preferably a closed cell foam. The invention also relates to foam,and preferably closed cell foam, prepared from a polymer foamformulation containing a blowing agent comprising an azeotrope-likecomposition of the invention.

In certain embodiments, one or more of the following HFC isomers arepreferred for use as co-blowing agents in the azeotrope-likecompositions of the present invention:

-   1,1,1,2,2-pentafluoroethane (HFC-125)-   1,1,2,2-tetrafluoroethane (HFC-134)-   1,1,1,2-tetrafluoroethane (HFC-134a)-   1,1-difluoroethane (HFC-152a)-   1,1,1,2,3,3,3-heptafluoropropane (HFC-227 ea)-   1,1,1,3,3,3-hexafluoropropane (HFC-236fa)-   1,1,1,3,3-pentafluoropropane (HFC-245 fa) and-   1,1,1,3,3-pentafluorobutane (HFC-365mfc).

The relative amount of any of the above noted additional co-blowingagents, as well as any additional components which may be included inthe present azeotrope-like compositions, can vary widely within thegeneral broad scope of the present invention according to the particularapplication for the composition, and all such relative amounts areconsidered to be within the scope hereof

Foams

The present invention also relates to all foams, including but notlimited to closed cell foam, open cell foam, rigid foam, flexible foam,integral skin and the like, prepared from a polymer foam formulationcontaining a blowing agent comprising an azeotrope-like compositioncomprising, or consisting essentially of, Z-HFO-1336mzzm and one or morealcohols, preferably methanol or ethanol. Applicants have found that oneadvantage of the foams, and particularly thermoset foams such aspolyurethane foams, in accordance with the present invention is theability to achieve, preferably in connection with thermoset foamembodiments, exceptional thermal performance, such as can be measured bythe k-factor or lambda, particularly and preferably under lowtemperature conditions, as shown in FIG. 1.

Although it is contemplated that the present foams, particularlythermoset foams of the present invention, may be used in a wide varietyof applications, in certain preferred embodiments the present inventioncomprises appliance foams in accordance with the present invention,including refrigerator foams, freezer foams, refrigerator/freezer foams,panel foams, and other cold or cryogenic manufacturing applications.

The foams prepared in accordance with the present invention, in certainpreferred embodiments, provide one or more exceptional features,characteristics and/or properties, including: thermal insulationefficiency (particularly for thermoset foams), dimensional stability,compressive strength, aging of thermal insulation properties, all inaddition to the low ozone depletion potential and low global warmingpotential associated with many of the preferred blowing agents of thepresent invention.

In certain highly preferred embodiments, the present invention providesthermoset foam, including such foam formed into foam articles, whichexhibit improved thermal conductivity relative to foams made using thesame blowing agent (or a commonly used blowing agent HFC-245fa) in thesame amount but without the azeotrope-like composition of the presentinvention.

Any of the methods well known in the art, such as those described inPolyurethanes Chemistry and Technology, Volumes I and II, Saunders andFrisch, 1962, John Wiley and Sons, New York, N.Y., which is incorporatedherein by reference, may be used or adapted for use in accordance withthe foam embodiments of the present invention. In general, suchpreferred methods comprise preparing polyurethane or polyisocyanuratefoams by combining an isocyanate, a polyol or mixture of polyols, ablowing agent or mixture of blowing agents comprising one or more of thepresent compositions, and other materials such as catalyst, as well assurfactants, and optionally, flame retardants, colorants, or otheradditives.

It is convenient in many applications to provide the components forpolyurethane or polyisocyanurate foams in pre-blended formulations. Mosttypically, the foam formulation is pre-blended into two components. Theisocyanate and optionally certain surfactants and blowing agentscomprise the first component, commonly referred to as the A component.The polyol or polyol mixture, surfactant, catalysts, blowing agents,flame retardant, and other isocyanate reactive components comprise thesecond component, commonly referred to as the B component. Accordingly,polyurethane or polyisocyanurate foams are readily prepared by bringingtogether the A and B side components either by hand mix for smallpreparations and, preferably, machine mix techniques to form blocks,slabs, laminates, pour-in-place panels and other items, spray appliedfoams, froths, and the like. Optionally, other ingredients such as fireretardants, colorants, auxiliary blowing agents, and even other polyolscan be added as a third stream to the mix head or reaction site. Mostconveniently, however, they are all incorporated into one B-component asdescribed above.

It is also possible to produce thermoplastic foams using theazeotrope-like compositions of the invention. For example, conventionalfoam polyurethanes and isocyanurate formulations may be combined withthe azeotrope-like compositions in a conventional manner to producerigid foams.

Dispersing agents, cell stabilizers, and surfactants may also beincorporated into the blowing agent mixture. Surfactants, most notablysilicone oils, are added to serve as cell stabilizers. Somerepresentative materials are sold under the names of DC-193, B-8404, andL-5340 which are, generally, polysiloxane polyoxyalkylene blockco-polymers such as those disclosed in U.S. Pat. Nos. 2,834,748,2,917,480, and 2,846,458. Other optional additives for the blowing agentmixture may include flame retardants such astri(2-chloroethyl)phosphate, tri(2-chloropropyl)phosphate,tri(2,3-dibromopropyl)-phosphate, tri(1,3-dichloropropyl)phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminum trihydrate, polyvinyl chloride, and the like.

In general, the amount of blowing agent present in the blended mixtureused to form the foamable composition of the present invention isdictated by the desired foam densities of the final polyurethane orpolyisocyanurate foams products. The polyurethane foams produced canvary in density from about 0.5 pound per cubic foot to about 40 poundsper cubic foot, preferably from about 1.0 to about 20.0 pounds per cubicfoot, and most preferably from about 1.5 to about 6.0 pounds per cubicfoot for rigid polyurethane foams and from about 1.0 to about 4.0 poundsper cubic foot for flexible foams. The density obtained is a function ofseveral factors, including how much of the blowing agent, or blowingagent mixture, is present in the A and/or B components, or that is addedat the time the foam is prepared.

Blowing Agent & Foam Example

This example demonstrates the performance of blowing agents comprisingZ-HF0-1336mzzm and alcohols used in connection with the preparation ofpolyurethane foams. Three separate blowing agents were prepared for thisexample. The first blowing agent is HFC-245fa. The second blowing agentis Z-HFO-1336mzzm. The third blowing agent comprises an azeotrope-likecomposition comprising Z-HFO-1336mzzm in a concentration ofapproximately 98 weight percent of the total blowing agent, and ethanolin a concentration of approximately 2 weight percent of the totalblowing agent.

In each system, the blowing agent was added in substantially the samemolar concentration into the polyol blend. Foams were then formed usingeach blowing agent and the k-factors of the foams are measured. Theformulation used is contained in the Table 6 below. The foams wereprepared with a 3 second pour time and a 8 second mix time. The rawmaterial temperatures were 50° F. polyol/70° F. MDI.

TABLE 6 Polyol Master Batch Composition Component php Manich polyetherpolyol, 80.00 OH 470 Aromatic polyester polyol 70.00 Diethylene glycol10.00 Silicone surfactant 2.00 Dimethyl ethanol amine 3.20 Neutralchlorinated 20.00 phosphate ester Water 2.00 Total 187.20 Moles blowingagent 0.698 Index 110

Table 7 below and FIG. 1 illustrate the k-factor performance of thethree blowing agents.

TABLE 7 k Factors of Polyurethane Foams 245 fa Z-HF0-1336mzzm + k,Z-HF0-1336mzzm 2 wt % ethanol Temp, BTU/ Temp, k, Temp, k, ° F. hr ft² °F. ° F. BTU/hr ft² ° F. ° F. BTU/hr ft² ° F. 40 0.132 40 0.137 40 0.13575 0.147 75 0.146 75 0.145 110 0.164 110 0.162 110 0.161

One unexpected result illustrated by this example is the improved lowtemperature k factor of the 98 wt % Z-HFO-1336mzzm and 2 wt % ethanolblend over that of the neat Z-HFO-1336mzzm blowing agent.

Spray Foams

In a spray foam example, it was surprisingly found that there was asignificant and unanticipated positive effect on the thermalconductivity of the foam by use of an azeotrope-like compositionconsisting essentially of 4 wt % of Z-HFO-1336mzzm and 96 wt %1233zd(E). The foams prepared with this blowing agent composition agedslower across all temperature ranges and had better thermal conductivityproperties than foams prepared with a blowing agent containing only1233zd(E).

Methods and Systems

The azeotrope-like compositions of the invention are also useful inconnection with numerous methods and systems, including as heat transferfluids in methods and systems for transferring heat, such asrefrigerants used in refrigeration, air conditioning and heat pumpsystems. The present azeotrope-like compositions are also advantageousfor in use in systems and methods of generating aerosols, preferablycomprising or consisting of the aerosol propellant in such systems andmethods. Methods of forming foams and methods of extinguishing andsuppressing fire are also included in certain aspects of the presentinvention. The present invention also provides in certain aspectsmethods of removing residue from articles in which the presentazeotrope-like compositions are used as solvent compositions in suchmethods and systems.

Heat Transfer Methods

The preferred heat transfer methods generally comprise providing anazeotrope-like composition of the present invention and causing heat tobe transferred to or from the composition by changing the phase of thecomposition. For example, the present methods provide cooling byabsorbing heat from a fluid or article, preferably by evaporating thepresent refrigerant composition in the vicinity of the body or fluid tobe cooled to produce vapor comprising the present composition.

Preferably the methods include the further step of compressing therefrigerant vapor, usually with a compressor or similar equipment toproduce vapor of the present composition at a relatively elevatedpressure. Generally, the step of compressing the vapor results in theaddition of heat to the vapor, thus causing an increase in thetemperature of the relatively high-pressure vapor. Preferably, thepresent methods include removing from this relatively high temperature,high pressure vapor at least a portion of the heat added by theevaporation and compression steps. The heat removal step preferablyincludes condensing the high temperature, high-pressure vapor while thevapor is in a relatively high-pressure condition to produce a relativelyhigh-pressure liquid comprising a composition of the present invention.This relatively high-pressure liquid preferably then undergoes anominally isoenthalpic reduction in pressure to produce a relatively lowtemperature, low-pressure liquid. In such embodiments, it is thisreduced temperature refrigerant liquid which is then vaporized by heattransferred from the body or fluid to be cooled.

In another process embodiment of the invention, the azeotrope-likecompositions of the invention may be used in a method for producingheating which comprises condensing a refrigerant composition comprising,or consisting essentially of, the azeotrope-like compositions of thisinvention, in the vicinity of a liquid or body to be heated. Suchmethods, as mentioned hereinbefore, frequently are reverse cycles to therefrigeration cycle described above.

Refrigerant Compositions

The azeotrope-like compositions of the present invention are adaptablefor use in connection with automotive air conditioning systems anddevices, commercial refrigeration systems and devices, chillers,residential refrigerator and freezers, general air conditioning systems,heat pumps, and the like.

Many existing refrigeration systems are currently adapted for use inconnection with existing refrigerants, and the azeotrope-likecompositions of the present invention are believed to be adaptable foruse in many of such systems, either with or without system modification.In many applications the azeotrope-like compositions of the presentinvention may provide an advantage as a replacement in systems, whichare currently based on refrigerants having a relatively high capacity.Furthermore, in embodiments where it is desired to use a lower capacityrefrigerant composition of the present invention, for reasons ofefficiency for example, to replace a refrigerant of higher capacity,such embodiments of the present compositions provide a potentialadvantage.

Thus, it is preferred in certain embodiments to use azeotrope-likecompositions comprising, or consisting essentially of, Z-HFO-1336mzzmand one or more alcohols, as a replacement for existing refrigerants,such as HCFC-123 or HFC-134a. In certain applications, the refrigerantsof the present invention potentially permit the beneficial use of largerdisplacement compressors, thereby resulting in better energy efficiencythan other refrigerants, such as HCFC-123 or HFC-134a. Therefore therefrigerant compositions of the present invention provide thepossibility of achieving a competitive advantage on an energy basis forrefrigerant replacement applications.

Although it is contemplated that the azeotrope-like compositions of thepresent invention may include the components in widely ranging amounts,it is generally preferred that refrigerant compositions of the presentinvention comprise, or consist essentially of, Z-HFO-1336mzzm, in anamount that is at least about 50% by weight, and even more preferably atleast about 70% by weight, of the composition.

Power Cycle Use

Raffl(ine cycle systems are known to be a simple and reliable means toconvert heat energy into mechanical shaft power. Organic working fluidsare useful in place of water/steam when low-grade thermal energy isencountered. Water/steam systems operating with low-grade thermal energy(typically 400° F. and lower) will have associated high volumes and lowpressures. To keep system size small and efficiency high, organicworking fluids with boiling points near room temperature are employed.Such fluids would have higher gas densities lending to higher capacityand favorable transport and heat transfer properties lending to higherefficiency as compared to water at low operating temperatures. Inindustrial settings there are more opportunities to use flammableworking fluids such as toluene and pentane, particularly when theindustrial setting has large quantities of flammables already on site inprocesses or storage. For instances where the risk associated with useof a flammable working fluid is not acceptable, such as power generationin populous areas or near buildings, other fluids such as CFC-113 andCFC-11 were used. Although these materials were non-flammable, they werea risk to the environment because of their ozone-depletion potential.Ideally, the organic working fluid should be environmentally acceptable,non-flammable, of a low order of toxicity, and operate at positivepressures.

As used herein, the term “nonflammable” refers to compounds andcompositions of the present invention which do not exhibit a flashpointas measured by one of the standard flash point methods, for exampleASTM-1310-86 “Flash point of liquids by tag Open-cup apparatus.”

Organic Rankine cycle systems are often used to recover waste heat fromindustrial processes. In combined heat and power (cogeneration)applications, waste heat from combustion of fuel used to drive the primemover of a generator set is recovered and used to make hot water forbuilding heat, for example, or for supplying heat to operate anabsorption chiller to provide cooling. In some cases, the demand for hotwater is small or does not exist. The most difficult case is when thethermal requirement is variable and load matching becomes difficult,confounding efficient operation of the combined heat and power system.In such an instance, it is more useful to convert the waste heat toshaft power by using an organic Rankine cycle system. The shaft powercan be used to operate pumps, for example, or it may be used to generateelectricity. By using this approach, the overall system efficiency ishigher and fuel utilization is greater. Air emissions from fuelcombustion can be decreased since more electric power can be generatedfor the same amount of fuel input.

The process that produces waste heat is at least one selected from thegroup consisting of fuel cells, internal combustion engines, internalcompression engines, external combustion engines, and turbines. Othersources of waste heat can be found in association with operations at oilrefineries, petrochemical plants, oil and gas pipelines, chemicalindustry, commercial buildings, hotels, shopping malls, supermarkets,bakeries, food processing industries, restaurants, paint curing ovens,furniture making, plastics molders, cement kilns, lumber kilns (drying),calcining operations, steel industry, glass industry, foundries,smelting, air-conditioning, refrigeration, and central heating. See U.S.Pat. No. 7,428,816, the disclosure of which is hereby incorporatedherein by reference.

One specific embodiment of a power cycle use of this compound is aprocess for recovering waste heat in an organic Rankine cycle system inwhich the working fluid is an azeotrope-like composition comprising, orconsisting essentially of, Z-HFO-1336mzzm and one or more alcohols,preferably methanol or ethanol.

Power Cycle Example

This example demonstrates the use of the azeotrope-like compositions ofthe present invention for use as a Rankine power cycle composition.

Following the procedure outlined in Smith, J. M. et al., Introduction toChemical Engineering Thermodynamics; McGraw-Hill (1996), theeffectiveness of various working fluids in an organic Rankine cycle canby compared. The conditions used in the organic Rankine cyclecalculations in this example are a pump efficiency of 75%, expanderefficiency of 80%, boiler temperature of 190° C., condenser temperatureof 45° C. and 1000 W of heat supplied to the boiler. The performance ofa 95:5 wt % mixture of Z-HFO-1336mzzm:methanol is compared to thecommercially available fluid HFC-245fa (available from Honeywell). Thethermal efficiency of HFC-245fa and 95:5 wt % mixture ofZ-HFO-1336mzzm:methanol at the conditions specified is 0.142 and 0.158,respectively. This shows that a 95:5 wt % mixture ofZ-HFO-1336mzzm:methanol would perform better than HFC-245fa in a powercycle.

Cleaning and Contaminant Removal

The present invention also provides methods of removing containmentsfrom a product, part, component, substrate, or any other article orportion thereof by applying to the article an azeotrope-like compositionof the present invention. For the purposes of convenience, the term“article” is used herein to refer to all such products, parts,components, substrates, and the like and is further intended to refer toany surface or portion thereof. Furthermore, the term “contaminant” isintended to refer to any unwanted material or substance present on thearticle, even if such substance is placed on the article intentionally.For example, in the manufacture of semiconductor devices it is common todeposit a photoresist material onto a substrate to form a mask for theetching operation and to subsequently remove the photoresist materialfrom the substrate. The term “contaminant” as used herein is intended tocover and encompass such a photo resist material.

Preferred methods of the present invention comprise applying the presentcomposition to the article. Although it is contemplated that numerousand varied cleaning techniques can employ the azeotrope-likecompositions of the present invention to good advantage, it isconsidered to be particularly advantageous to use the presentcompositions in connection with supercritical cleaning techniques.Supercritical cleaning is disclosed in U.S. Pat. No. 6,589,355, which isassigned to the assignee of the present invention and incorporatedherein by reference.

For supercritical cleaning applications, it is preferred in certainembodiments to include in the present cleaning compositions, in additionto the azeotrope-like composition of the present invention, anothercomponent, such as CO₂ and other additional components known for use inconnection with supercritical cleaning applications.

It may also be possible and desirable in certain embodiments to use thepresent cleaning compositions in connection with particular sub-criticalvapor degreasing and solvent cleaning methods.

Another cleaning embodiment of the invention comprises the removal ofcontaminants from vapor compression systems and their ancillarycomponents when these systems are manufactured and serviced. As usedherein, the term “contaminants” refers to processing fluids, lubricants,particulates, sludge, and/or other materials that are used in themanufacture of these systems or generated during their use. In general,these contaminants comprise compounds such as alkylbenzenes, mineraloils, esters, polyalkyleneglycols, polyvinylethers and other compoundsthat are made primarily of carbon, hydrogen and oxygen. Theazeotrope-like compositions of the present invention will be useful forthis purpose.

Cleaning Composition Example

This example demonstrates the use of the azeotrope-like compositions ofthe present invention for use as a cleaning composition.

Azeotrope-like compositions are prepared containing 95% by weightZ-HFO-1336mzzm with about 5% by weight ethanol. Several stainless steelcoupons are soiled with mineral oil, rosin flux or other contaminants.Then these coupons are then immersed in the solvent blend. The blendcould remove the oils in a short period of time. The coupons areobserved visually for cleanliness. Similar results are expected with theother mixtures. Similar results are also expected with silicon oil.

Propellants for Sprayable Compositions

In another embodiment, the azeotrope-like compositions of this inventionmay be used as propellants in sprayable compositions, either alone or incombination with known propellants. The propellant compositioncomprises, more preferably consists essentially of, and, even morepreferably, consists of the azeotrope-like compositions of theinvention. The active ingredient to be sprayed together with inertingredients, solvents, and other materials may also be present in thesprayable mixture. Preferably, the sprayable composition is an aerosol.Suitable active materials to be sprayed include, without limitation,lubricants, insecticides, cleaners, cosmetic materials such asdeodorants, perfumes and hair sprays, polishing agents, as well asmedicinal materials such as skin cooling agents (sunburn treatment),topical anesthetics and anti-asthma medications.

The sprayable composition includes a material to be sprayed and apropellant including the azeotrope-like compositions of this invention.Inert ingredients, solvents, and other materials may also be present inthe sprayable mixture. Preferably, the sprayable composition is anaerosol. Suitable materials to be sprayed include, without limitation,cosmetic materials such as deodorants, perfumes, hair sprays, cleansers,and polishing agents as well as medicinal materials such as anti-asthmaand anti-halitosis medications.

Sterilization

Many articles, devices and materials, particularly for use in themedical field, must be sterilized prior to use for the health and safetyreasons, such as the health and safety of patients and hospital staff.The present invention provides methods of sterilizing comprisingcontacting the articles, devices or material to be sterilized with anazeotrope-like composition of the present invention, and optionally incombination with one or more additional sterilizing agents.

While many sterilizing agents are known in the art and are considered tobe adaptable for use in connection with the present invention, incertain preferred embodiments sterilizing agent comprises ethyleneoxide, formaldehyde, hydrogen peroxide, chlorine dioxide, ozone andcombinations of these. In certain embodiments, ethylene oxide is thepreferred sterilizing agent. Those skilled in the art, in view of theteachings contained herein, will be able to readily determine therelative proportions of sterilizing agent and the present compound(s) tobe used in connection with the present sterilizing compositions andmethods, and all such ranges are within the broad scope hereof.

As is known to those skilled in the art, certain sterilizing agents,such as ethylene oxide, are extremely flammable components, and thecompound(s) in accordance with the present invention are included in thepresent compositions in amounts effective, together with othercomponents present in the composition, to reduce the flammability of thesterilizing composition to acceptable levels. The sterilization methodsof the present invention may be either high or low-temperaturesterilization of the present invention involves the use of a compound orcomposition of the present invention at a temperature of from about 250°F. to about 270° F., preferably in a substantially sealed chamber. Theprocess can be completed usually in less than about two hours. However,some articles, such as plastic articles and electrical components,cannot withstand such high temperatures and require low-temperaturesterilization.

Sterilization Examples

In low temperature sterilization methods, the article to be sterilizedis exposed to a fluid comprising a composition of the present inventionat a temperature of from about room temperature to about 200° F., morepreferably at a temperature of from about room temperature to about 100°F.

The low-temperature sterilization of the present invention is preferablyat least a two-step process performed in a substantially sealed,preferably air tight, chamber. In the first step (the sterilizationstep), the articles having been cleaned and wrapped in gas permeablebags are placed in the chamber.

Air is then evacuated from the chamber by pulling a vacuum and perhapsby displacing the air with steam. In certain embodiments, it ispreferable to inject steam into the chamber to achieve a relativehumidity that ranges preferably from about 30% to about 70%. Suchhumidities may maximize the sterilizing effectiveness of the sterilant,which is introduced into the chamber after the desired relative humidityis achieved. After a period of time sufficient for the sterilant topermeate the wrapping and reach the interstices of the article, thesterilant and steam are evacuated from the chamber.

In the preferred second step of the process (the aeration step), thearticles are aerated to remove sterilant residues. Removing suchresidues is particularly important in the case of toxic sterilants,although it is optional in those cases in which the substantiallynon-toxic compounds of the present invention are used. Typical aerationprocesses include air washes, continuous aeration, and a combination ofthe two. An air wash is a batch process and usually comprises evacuatingthe chamber for a relatively short period, for example, 12 minutes, andthen introducing air at atmospheric pressure or higher into the chamber.

As used herein the term “non-toxic” refers to compounds and compositionsof the present invention which have an acute toxicity levelsubstantially less than, and preferably at least about 30 relativepercent less than, the toxicity level of HFO-1223xd, as measured by themethod published in Anesthesiology, Vol. 14, pp. 466-472, 1953,incorporated here by reference.

This cycle is repeated any number of times until the desired removal ofsterilant is achieved. Continuous aeration typically involvesintroducing air through an inlet at one side of the chamber and thendrawing it out through an outlet on the other side of the chamber byapplying a slight vacuum to the outlet. Frequently, the two approachesare combined. For example, a common approach involves performing airwashes and then an aeration cycle.

Lubricants

In certain preferred embodiments, the azeotrope-like compositions of thepresent invention can further comprise a lubricant. Any of a variety ofconventional lubricants may be used in the azeotrope-like compositionsof the present invention. An important requirement for the lubricant isthat, when in use in a refrigerant system, there must be sufficientlubricant returning to the compressor of the system such that thecompressor is lubricated. Thus, suitability of a lubricant for any givensystem is determined partly by the refrigerant/lubricant characteristicsand partly by the characteristics of the system in which it is intendedto be used.

Examples of suitable lubricants include mineral oil, alkyl benzenes,polyol esters, including polyalkylene glycols, PAG oil, and the like.Mineral oil, which comprises paraffin oil or naphthenic oil, iscommercially available. Commercially available mineral oils includeWitco LP 250 (registered trademark) from Witco, Zerol 300 (registeredtrademark) from Shrieve Chemical, Sunisco 3GS from Witco, and CalumetR015 from Calumet. Commercially available alkyl benzene lubricantsinclude Zerol 150 (registered trademark). Commercially available estersinclude neopentyl glycol dipelargonate which is available as Emery 2917(registered trademark) and Hatcol 2370 (registered trademark). Otheruseful esters include phosphate esters, dibasic acid esters, andfluoroesters. Preferred lubricants include polyalkylene glycols andesters. Certain more preferred lubricants include polyalkylene glycols.

Extraction of Flavors and Fragrances

The azeotrope-like compositions of the present invention also provideadvantage when used to carry, extract or separate desirable materialsfrom biomass. These materials include, but are not limited to, essentialoils such as flavors and fragrances, oils which may be used as fuel,medicinals, nutraceuticals, etc.

Extraction Example

The suitability of the azeotrope-like compositions of the presentinvention for this purpose is demonstrated by a test procedure in whicha sample of Jasmone is put into a heavy walled glass tube. A suitableamount of the azeotrope-like composition of the present invention isadded to the glass tube. The tube is then frozen and sealed. Uponthawing the tube, when the mixture has one liquid phase containingJasmone and the azeotrope-like composition; this test establishes thefavorable use of the composition as an extractant, carrier or part ofdelivery system for flavor and fragrance formulations, in aerosol andother formulations. It also establishes its potential as an extractantof flavors and fragrances, including from plant matter.

Flammability Reduction Methods

According to certain other preferred embodiments, the present inventionprovides methods for reducing the flammability of fluids, said methodscomprising adding an azeotrope-like composition of the present inventionto said fluid. The flammability associated with any of a wide range ofotherwise flammable fluids may be reduced according to the presentinvention. For example, the flammability associated with fluids such asethylene oxide, flammable hydrofluorocarbons and hydrocarbons,including: HFC-152a, 1,1,1-trifluoroethane (HFC-143a), difluoromethane(HFC-32), propane, hexane, octane, and the like can be reduced accordingto the present invention. For the purposes of the present invention, aflammable fluid may be any fluid exhibiting flammability ranges in airas measured via any standard conventional test method, such as ASTME-681, and the like.

Any suitable amounts of the present compounds or compositions may beadded to reduce flammability of a fluid according to the presentinvention. As will be recognized by those of skill in the art, theamount added will depend, at least in part, on the degree to which thesubject fluid is flammable and the degree to which it is desired toreduce the flammability thereof. In certain preferred embodiments, theamount of compound or composition added to the flammable fluid iseffective to render the resulting fluid substantially non-flammable.

Flammability Reduction Example

This example demonstrates the use of the azeotrope-like compositions ofthe present invention for reduction of flammability of anothercomposition.

In an ASTM E681 apparatus at ambient conditions, one mixes isopentanevapor and the azeotrope like mixture of 97:2 wt % Z-HFO-1336mzzm:ethanolto find that the lower flammability limit (LFL) increases as more of theazeotrope like mixture of 97:2 wt Z-HFO-1336mzzm:ethanol is added. Thisindicates lower flammability for the blend than that of the isopentaneby itself leading; a less flammable material which is easier to usesafely. This higher LFL allow higher concentration in air withoutconcern for ignition source and potential fires or explosions.

Two aerosol cans are filled with methanol/water and one is pressurizedwith HFC-152a while the other is pressurized with HFC-152a and anazeotrope like mixture of 97:2 wt Z-HFO-1336mzzm:ethanol. When theaerosols from the cans are sprayed over and into a candle flame as inthe aerosol flame extension test procedure one observe less flameextension from the can that is pressured with an azeotrope like mixtureof 97:2 wt % Z-HFO-1336mzzm:ethanol.

Flame Suppression Methods

The present invention further provides methods of suppressing a flame,said methods comprising contacting a flame with an azeotrope-likecomposition of the present invention. If desired, additional flamesuppressing agents can also be used with the composition of the presentinvention, either in admixture, or as a secondary flame suppressingagent. One class of compounds useful for this purpose is thefluoroketones. One especially preferred fluoroketone isdodecafluoro-2-methylpentan-3-one. One commercial source for thispreferred compound is the 3M Company under the trade name Novec 1230.

Any suitable methods for contacting the flame with the presentcomposition may be used. For example, a composition of the presentinvention may be sprayed, poured, and the like onto the flame, or atleast a portion of the flame may be immersed in the composition.

While the present invention has been particularly shown and describedwith reference to preferred embodiments, it will be readily appreciatedby those of ordinary skill in the art that various changes andmodifications may be made without departing from the scope of theinvention. It is intended that the claims be interpreted to cover thedisclosed embodiment, those alternatives which have been discussed aboveand all equivalents thereto.

What is claimed is:
 1. An azeotrope-like composition comprisingeffective amounts of from greater than zero to about 99 wt % of thecompound cis-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzzm) and fromabout 1 wt % to less than 100 wt % of another material selected from thegroup consisting of water, fluoroketones, alcohols,hydrochloro-fluoroolefins, and combinations of two or more thereof 2.The azeotrope-like composition of claim 1 comprising effective amountsof from about 85 wt % to less than 100 wt % of Z-HFO-1336mzzm and fromgreater than zero to about 15 wt % of an alcohol, and combinations oftwo or more thereof.
 3. The azeotrope-like composition of claim 1comprising effective amounts of from greater than zero to about 50 wt %of water and from about 50 wt % to less than 100 wt % of Z-HFO-1336mzzm.4. The azeotrope-like composition of claim 1 comprising effectiveamounts of from 50 wt % to about 99 wt % of Z-HFO-1336mzzm and fromabout 1 wt % to less than 50 wt % of a fluoroketone.
 5. Theazeotrope-like composition of claim 1 comprising effective amounts offrom about 1 wt % to about 99 wt % of Z-HFO-1336mzzm and from about 1 wt% to about 99 wt % of trans-1,1,1-trifluoro-3-chloropropene.
 6. Ablowing agent comprising an azeotrope-like composition of claim
 1. 7. Amethod of forming a foam comprising adding to a foamable composition ablowing agent comprising an azeotrope-like composition of claim
 1. 8. Apremix of a polyol and a blowing agent wherein the blowing agentcomprises an azeotrope-like composition of claim
 1. 9. A closed cellfoam prepared by foaming a foamable composition in the presence of ablowing agent comprising the azeotrope-like composition of claim
 1. 10.A refrigerant composition comprising an azeotrope-like composition ofclaim
 1. 11. A refrigeration system comprising a refrigerant compositionof claim
 10. 12. A method for cooling an article which comprisesevaporating a refrigerant composition of claim 10 in the vicinity of thearticle to be cooled.
 13. A method for heating an article whichcomprises condensing a refrigerant composition of claim 10 in thevicinity of the article to be heated.
 14. A sprayable compositioncomprising a material to be sprayed and a propellant comprising anazeotrope-like composition of claim
 1. 15. A method for sterilizing anarticle which comprises treating the article to be sterilized with anazeotrope-like composition of claim
 1. 16. A method of extractingflavors or fragrances from biomass which comprises treating the biomasswith an azeotrope-like composition of claim
 1. 17. A method ofsterilizing an article, said method comprising contacting said articleto be sterilized with a composition comprising an azeotrope-likecomposition of claim
 1. 18. A method of suppressing a flame comprisingcontacting said flame with a fluid comprising an azeotrope-likecomposition of claim
 1. 19. A centrifugal chiller working fluidcomprising an azeotrope-like composition of claim
 1. 20. A power cycleworking fluid comprising an azeotrope-like composition of claim 1.